Binding and Electronic Level Alignment of $\mathbf{\pi }$-Conjugated Systems on Metals

Abstract

We review the binding and energy level alignment of $\pi$-conjugated systems on metals, a field which during the last two decades has seen tremendous progress both in terms of experimental characterization as well as in the depth of theoretical understanding. Precise measurements of vertical adsorption distances and the electronic structure together with \textit{ab-initio} calculations have shown that most of the molecular systems have to be considered as intermediate cases between weak physisorption and strong chemisorption. In this regime, the subtle interplay of different effects such as covalent bonding, charge transfer, electrostatic and van der Waals interactions yields a complex situation with different adsorption mechanisms. In order to establish a better understanding of the binding and the electronic level alignment of $\pi$-conjugated molecules on metals, we provide an up-to-date overview of the literature, explain the fundamental concepts as well as the experimental techniques and discuss typical case studies. Thereby, we relate the geometric with the electronic structure in a consistent picture and over the entire range from weak to strong coupling.

arXiv comment50 pages, 28 figures, 2 tables peer-reviewed version, accepted by Reports on Progress in Physics

References in corpus (34)

• Van der Waals Density Functional for General Geometries
• Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory
• van der Waals forces in density functional theory: The vdW-DF method
• Van der Waals Density Functional for Layered Structures
• Reversible Photomechanical Switching of Individual Engineered Molecules at a Surface
• The trap DOS in small molecule organic semiconductors: A quantitative comparison of thin-film transistors with single crystals
• Molecular Electronics by Chemical Modification of Semiconductor Surfaces
• Noncovalent Functionalization of Black Phosphorus
• Imaging Pauli repulsion in scanning tunneling microscopy
• Adsorption structures and energetics of molecules on metal surfaces: Bridging experiment and theory
• Direct Experimental Evidence for the Hybridization of Organic Molecular Orbitals with Substrate States at Interfaces: PTCDA on Silver
• Substrate dependent bonding distances of PTCDA - A comparative XSW study on Cu(111) and Ag(111)
• Adsorption-Induced Distortion of F_{16}CuPc on Cu(111) and Ag(111): An X-ray Standing Wave Study
• Approaching ideal graphene: The structure of hydrogen-intercalated graphene on 6H-SiC(0001)
• Theory and Applications of X-ray Standing Waves in Real Crystals
• Energy Level Alignment at Molecule-Metal Interfaces from an Optimally-Tuned Range-Separated Hybrid Functional
• Accurate description of charged excitations in molecular solids from embedded many-body perturbation theory
• Interface dipoles of organic molecules on Ag(111) in hybrid density-functional theory
• First-principles study of the dipole layer formation at metal-organic interfaces
• Exploring the Bonding of Large Hydrocarbons on Noble Metals: Diindoperylene on Cu(111), Ag(111), and Au(111)
• Orientational Ordering of Nonplanar Phthalocyanines on Cu(111): Strength and Orientation of the Electric Dipole Moment
• Orbital tomography of hybridized and dispersing molecular overlayers
• Model potential for the description of metal/organic interface states
• Quantification of finite-temperature effects on adsorption geometries of $\pi$-conjugated molecules
• Bistability loss as key feature in azobenzene (non-)switching on metal surfaces
• Interpretation of X-ray Absorption Spectroscopy in the Presence of Surface Hybridization
• van der Waals density functional with corrected $C_6$ coefficients
• The role of the van der Waals interactions in the adsorption of anthracene and pentacene on the Ag(111) surface
• Symmetry, Shape and Energy Variations in Frontier Molecular Orbitals at Organic/Metal Interfaces: the Case of F${}_4$TCNQ
• Adsorption structure determination of a large polyaromatic trithiolate on Cu(111): combination of LEED-I(V) and DFT-vdW
• Structure and vibrational properties of the PTCDA/Ag(111) interface: Bilayer vs. monolayer
• Effects of different electron-phonon couplings on spectral and transport properties of small molecule single-crystal organic semiconductors
• Adsorption-induced symmetry reduction of metal-phthalocyanines studied by vibrational spectroscopy
• Adsorption geometry and electronic properties of flat-lying monolayers of tetracene on the Ag(111) surface

Cited by in corpus (3)

• Robust Dipolar Layers between Organic Semiconductors and Silver for Energy-Level Alignment
• Can we predict interface dipoles based on molecular properties?
• Upper Bound Estimate of the Electronic Scattering Potential of a Weakly Interacting Molecular Film on a Metal